Polyazo dyestuffs



Patented Jan. 16, 1951 .UNITED STATES PATENT oFF c 2,538,180 I POLYAZO DYE STUFFS cm, i, a i, g i i Willy WIdmer, Bottmingen, Switzerland, assignor E Me. a. J

to Ciba Limited, Basel,

' N0 Drawing. Application March 31, 1947, Serial No. 738,489. In Switzerland April 16, 1946 i 7 Claims. (Cl. 260160) According to this invention valuable new polyazo-dyestuffs free from sulfonic acid groups are made by using as a coupling component a compound of the general formula in which R1 represents the radical of a diphenyl 1. bound in the 4- and 4'-positions to Pm and Pyz, and Pyi and Pyz each represent the radical of a pyrazolone bound in the 1-position to the diphenyl radical, and using at least once as a diazo-component a diazo-compound of an amine of the general formula in which R2 represents a benzene radical, X'represents a group occupying a position vicinal to the -NH2 group and capable of taking part in the formation of heavy metal complexes, and Y represents an acid amide group bound by the. aci dradical to R2, and, if desired, treating the resulting dyestuff with an agent yielding metal. Among the coupling components of the above generalformula Py1-R1-Pyz, which are used as starting materials in the process of the invention, there cnme into consideration those in which the diphenyl radical R1 is free from further substituents, and also those which contain further substituents, in the diphenyl radical, for example, alkyl groups such as a methyl group, alkoxy groups such as a methoxy group, or halogen atoms such as chlorine. In the latter case the same substituent may be present twice or more in the diphenyl radical, or the substituents may differ from one another, and each individual substituent may be present once or more than once. As examples of such coupling components there may be mentioned, among others, those in which the radical R1 represents thev following radicals: 3:3 dimethyldiphenyl-, 3:3 dimethoxydiphenyl-, 3:3 dichlorodiphenyland principally the unsubstituted diphenyl residue. The two pyrazolone radicals Pyi and Py2 present in the coupling components of the above formula may, for example, differ from one another. It is of advantage to use coupling components which contain the same pyrazolone radical twice. The pyrazolone radicals may contain a substituent in the 3-position,

for example, a carboxyl group. There come principally into consideration, however, compounds which contain in; that position an alkyl group, especially a methyl group. As example Switzerland, a Swiss JUN 12 1951..

2 of coupling components which can be used with advantage as starting materials in the process of: the invention there may be mentioned dip'yrazolones obtained from 1 molecular proportion of 4:4-diaminodiphenyl or 3:3'-dichl0r0- 4:4-diaminodiphenyl and 2 molecular proportions of acetoacetic acid ester or oxalyl acetic acid ester (the pyrazolones being obtained in the usual manner by tetrazotizing the diaminodiphenyl-compound, reducing the product to the corresponding dihydrazine, and condensing the latter with acetoacetic acid ester or oxalyl acetic acid ester). Especially valuable dyestuffs can be obtained, for example, with the dipyrazolone from 4:4'-diaminodiphenyl and acetoacetic acid es er.

In the diazo-compounds of amines of the general formula I NHi also used as starting materials in the present process, X represents a group occupying a position vincinal to the NH2- group and capable of taking part in the formation of heavy metal complexes, for example, a carboxyl group or a methoxy group. Especially valuable results can be obtained with those diazo-components which contain in that position a hydroxyl group. The substituent Y in the diazo-components of the above formula represents an acid amide group, for example, a carboxylic acid amide group or a sulfonamide group. The nitrogen atom in the acid amide group may be free from substituents, or may have one or two substituents, for example, one or two alkyl radicals such as methyl and/or ethyl, or an aryl radical, or' an aryl racii cal and an alkyl radical, a benzene radical com-" ing principally into,consideration as an aryl radical and which benzene radical may, if desired, carry further substituents. The acid amide group Y may occupy any desired position'in the benzene radical R2. However, owing to their easy accessibility there come into consideration especially those diam-components in which the acid amide group is in the 4-position' relatively to the'group X and principally when the 'X represents an alkoxy or hydroxyl group. In addition to the -NH2, X and -Y groups, the benzene radical R2 may contain further sub stituents, for example a nitro group, an alkyl group such as methyl, or a halogen atom suchaschlorine. 'As examples of diazo-components of-theabove formula there may be mentioned;

2-amino-1-hydroxy 4 benzanilide, 2 aminol-hydroxy-G-chloro 4 benzanilide, 2-aminol-hydroxyl-chloro 6 benzanilide, 2-amino- 1 hydroxy-i-nitro 6 benzanilide, 2 amino- 1-hydroxy-4-benzoic acid-(4=-dimethylsulfonylphenylanilide) 2 amino-1-hydroxy-4-sulfonic acid anilide, Z-amino-l-hydroxyi-sulfonic acid methyl-anilide, 2 amino-'1-methoxy-4-sulfonic acid anilide and 2-amino-1-(p-carboxy-methoxy-) -4-benzanilide.

Especially valuable dyestuffs can be obtained by using as starting materials in the present process diazo-compounds of amines f the general formula HzNOzS-Ra in which R2 represents a benzene radical and the groups --NH2 and OH occupy positions vicinal to one another. Such amines are, for example, 6-chloro 2 amino-1-hydroxybenzene-4-sulfonamide, 6 nitro 2 amino-l-hydroxybenzene-isulfonamide, 6 methyl-Z-amino-l-hydroxybenzene-4-sulfonamide and principally 2-amino-1- hydroxybenzene-4-sulfonamide.

By the present process there may be produced, for example, asymmetrical polyazo-dyestuffs by coupling 1 molecular proportion of a coupling component of the formula first mentioned above, on the one hand, with 1 molecular proportion of a diazo-compound of an amine of the general formula in which R2, X and Y have the meanings given above and, on the other, with 1 molecular proportion of any desired diazo-component. As the second diazo-component there is advantageously chosen one which, even when it contains no acid amide group, likewise contains as a substituent in ortho-position relatively to the diazotizable amino-group a group capable of taking part in the formation of heavy metal complexes. The second diazo-component may also be a diazotized aminoazo-dyestuff. Examples of such diazo components are: 1-aminobenzene-Z-carboxylic acid, 1-amino-2-phenoxy-acetic acid, 4-amino- 4-hydroxy-1:1'-azobenzene 3:3 dicarboxylic acid.

It is of especial advantage in the present process to couple 1 molecular proportion of a coupling component of the formula first mentioned above with 2 molecular proportions of a diazo-compound of an amine of the general formula in which R2, Y and X have the meanings given above, whereby symmetrical disazo-dyestufis are obtained, provided that the coupling component is symmetrical.

The coupling reaction may be conducted in an acid, neutral or advantageously an alkaline medium. When asymmetrical dyestuffs are made by the present process by coupling 1 molecular proportion of a dipyrazolone of the formula first mentioned above with 1 molecular proportion of two different diazo-compounds, it is recommended to conduct the first coupling with one diazo-component in an acid medium, advantageously a medium rendered acid with acetic acid, and then the coupling with the other diazocomponent in an alkaline medium it is in most cases of advantage to dissolve the coupling component with the aid of a small excess of an alkali hydroxide so that it is present in the form of its di-alkali salt, and to add the further quantity of alkali required for coupling in the form, for example, of an alkali carbonate. The working up of the resulting dyestuffs is carried out in a manner in itself known, for example, by filtration and drying.

The polyazo-dyestufis free from sulfonic acid groups obtainable by the present process are new and correspond to the general formula in which R1 represents the radical of a diphenyl bound in the 4- and 4-positions to Pyl and Pyz, FYI and Pyz each represent the radical of a pyrazolone bound in the 1-position to the diphenyl radical and in the 4-position to the -N=N group, and R3 and R4 each represent the radical of a diazo-component of which at least one corresponds to the general formula in which R2 represents a benzene radical, X represents a group occupying a position vicinal to the NH2 group and capable of taking part in the formation of heavy metal complexes, and Y represents an acid amide group bound by the acid 'radicalto R2.

The polyazo-dyestuffs obtained by the present process are suitable for dyeing a very wide variety of materials, especially cellulose fibers such as cotton and artificial silk and staple fibers of regenerated cellulose, and also animal fibers such as wool, silk and leather. They can be converted in substance, in the dyebath or on the fiber into complex metal compounds, for example, copper, chromium, iron, nickel or cobalt compounds. The conversion into such complex metal compounds, which may contain a plurality of metals in the complex, is carried out by the known methods in an acid, neutral or alkaline solution with or without suitable additions such as salts of inorganic or organic acids, salts of acids forming complexes such as tartaric acid or aminoacetic acid, in the presence or absence of a diluent or suspending medium such as pyridine or glycerine, and under atmospheric or super-atmospheric pressure. Furthermore, many of the, complex metal compounds produced in substance, especially cobalt and/or nickel compounds, can be used for coloring masses and solutions thereof, such as nitrocellulose lacquers, artificial resins and spinning masses.

Notwithstanding that the polyazo-dyestuffs of the invention contain no sulfonic acid groups they generally have an adequate solubility and a good affinity for cellulose fibers in the metalfree condition. They may with advantage be treated on the fiber or in the dyebath or partlyv on the fiber and partly in the dyebath by known methods with agents yielding metal. It is, however, of advantage to use the process described in U. S. Patent No. 2,148,659, in which the material is first dyed and then treated in the same bath with an agent yielding metal. As agents yielding metal there come into consideration preferably v the diam-compound disappears. The dyestuff of the fprmulw. v-

those which sesa e towardsalkaline solutioris, such as complex copper tartrates and the like;

HnNOzS 3 CH: SO2NH:

. H 3 O-CHa HA) In U. S. Patent No. 2,228,374 there are described after being separated and dried in a red-brown polyazo-dyestufis obtained from 1:1'-[ diphenylpowder which dissolves in'concentrated sulfuric ene-(4z4) l-bis-(3-methyl 5 pyrazolone) and acid with a yellow coloration and in dilute alkavarious diam-components. These dyestuffs in all line with fan orange-yellow coloration, and dyes cases contain groups imparting solubility-such as cellulose fibers by the single' bath or two-bath sulfonic acid groups and/or carboxyl groups; but after-coppering process fast reddish yellow tints. in no case a sulfonamide group. As compared Dyestuffs having similar properties are 0bwith these known dyestuffs the new dyestuffs of tained by starting from l-aminobenzene-2-carthe present invention "containing sulfonamide boxylic aci'dfor l-amino-2-phenoxyacetic acid or groups have important advantages, for example, 4-amino-l'-hydroxy l:1'- azob'enzene 3:3 dithey yield dyeings offlbetter fastness to washing carboxylic acid instead of from l-nlethoxy-Z- and/or they have a better affinity towards celluarninobenzene-4-sulfonamide, and proceeding aclose fibers. cording tothe'da'ta of this example.

The following examples illustrate the mven- Example tion, the parts being by weight: e

Ewambze 1 4.6 parts 'ofl-hydroxy-2-amino-benzene-4- carboxylic acid anillde are diazotized in the usual 3.76 parts of 2-amino-1-hydroxybenzene-4-sulmanner in solution in hydrochloric acid. The refonamide are diazotized in the usual manner in sulting suspension of the diazo-compound is neua hydrochloric acid solution. The resulting su's- H pension of the diam-compound is neutralized by v3o with a solution of 3.5 parts of 1:1. -[diphenylenethe addition of sodium carbonate, and coupled (414')]-bis-(3-methyl-5-pyrazolone) in 40 parts with a solution of 3.6 parts'of 1:1'-[diphenyleneof caustic soda solution of 2.5 per cent. strength (4:4') lbis-(3-methyl-5-pyrazolone) in 40 parts and 10 parts of sodium carbonate solution of 10 of a caustic soda solution of 2.5 per cent. strength per cent. strength. When coupling is complete and 10 parts of a sodium carbonate solution of it) the dyestufi of the formula 4 a is separated by filtering, and dried. It is a redbrown powder which dissolves in concentrated per cent. strength. When the coupling is complete the precipitated dyestuff of the formula H3CC=N N=C-CH 111N028 SOzNHz 5 N N l i is separated by filtration and dried. It is an sulfuric acid with a yellow coloratio and dyes orange-brown powder, which dissolves in hot cellulose fibers by the single-bath or 2-bath afterwater with an orange-yellow coloration, and dyes coppering process fast yellow brown tints. A simcellulose fibers by the; single bath or two-bath ilar dyestufi, which dyes somewhat more yellowafter-coppering process reddish yellow tints ish tints, is obtained by starting from the comwhich are especially fast to washing and light. pound of the formula 33 Example 2 2 parts of 1-methoxy-2-aminobenzene-4-sul+ fonamde are diazotized in the usual manner in a hydrochloric acid solution, and then stirred with a suspension, rendered acid with, acetic acid a and containing sodium acetate, of 3.5'parts of 1:1- [diphemylene-(424') l-bis-(S methyl-5-pyrazolone) while cooling with ice until the diazocompound can no longer be detected. The product is then coupled with the diam-compound ob- 7o tained by diazotizing 119. parts of 1-hydroxy-2- aminobenzene-4-sulfonamide and neutralization with sodium carbonate, a quantity of sodium cara I bonate solution is added suflicient to give a dis- 7 tinctly alkaline reaction with Brilliant Yellow pa n i J penand the whole isstirred while cooling until NW3!" Olili traliaed with sodium carbonate, and then coupled Meat-sq; 7

. examp e.

we 'naraust is ae ii per 1 cent trength; and-;thewhole-ismixed 'with, an Parts the the alkaline solutibn of compiex-sodmm-eebau tartrate in a quantity correspondin to 5.9 parts 5 of cobalt. The whole'is heated for a short time at 6Q-70 and the cobalt compound so "formed 'is precipitated by neutralization with acetic acid, separated by filtration, and dried under reduced pressure. 4 parts of the resulting v i 10: complexcobaltcompound of the dyestufi, when N-OH; dissolved; in1000 parts of an ordinary commercialnitrocellulose lacquer, yield a coatingpom positionwith which yellow coatings which are.

- fast to light can be produced on a suitable sup-1 .,15 port I E qmp are diazotized in theusual manner in solution -in hydrochloric acid.- The resulting suspension fllOO partsoficotton'are entered at 40 fC.,into

of the diazo-compound is neutralized with so-l a dyebath which contians 0.6 part .of the vdyestuff dium carbonate, and coupled with a solution of obtained as describedv in Example 1. and "3 partsv 3.5 parts of l1l-[diphenylene-(4:4').]-bis (3-. of sodiumcarbonatein 3000 parts of water, the methy1-5-pyrazo1one) in 40 parts of caustic soda temperature is raised to 90-95 0;, parts of solution at 2.5 per cent. strength and 10 parts Glauber salt are added,.and dyeing is carried of sodium carbonate solution of 10 per cent. on my. hour at 9095 C. The dyebath is then strength. When the coupling is complete the 25 cooled to 80 C., the necessary quantity of a'comdyestuff of the formula plex copper tartrate -solution rendered weakly m n w a. i I r i a.

1 $11 H 5 I I .3,

is separated by filteringi and dried; It is aredalkaline with sodium carbonate, and containing. brown powder which dissolves in concentrated 0.2 part of copper bound in complex union, is sulfuric acid with a yellow-coloration in a ;l ded, and-theeotton is treated for /show at wafer with an orange-brown coloration, and, 80:90 C. It is then thoroughly rinsed and if dyes cellulose fibers by the singl-bath...or '2- q .desired soap ed for a short time. Thecotton is bath after-coppering process fast reddish yel- 40 dyed a fast yellow tint.

low tints. Similar dyestufis are obtained by What I claim is: using, instead of the above named diazo-coml. A polyazo dyestuff which is free from sulponent, a diazo-compound of an amine of one ionic acid groups and corresponds to the formula of the following formulae v 1 modem I i NH I g j =C Y'VM M v C: NY=NVRA I i no. on

' in which R3 and R4 each stands for the radical of a diazo component of the benzene series containing in ortho-position' to the NH2 group NE a substituent which participates in the formation of; heavy metal complexes, at least one of these -diazo components corresponding to the formula in which R2 stands for'a benzene radical carrying the OI-I-' and 'NHz-' groups in orthoposition'to one another and Y stands for an acid amide group bound'by the acid radical to R2 and selected from the class consisting of carboxylic acid amide and sulfonic acid amide groups. 2. A disazo-dyestu'ff which is free from sulfonic acid groups and corresponds to the formula 7.44 parts of the dyestuff obtained as described in which Rastands'for a benzene radical in which in Example 1 are dissolved in 100 parts of water ;the, N ;N and the -OH groups occupy posi tions vicinal to one another and Y stands for a I carboxylic acid amide group bound by the acid radical to R2.

3. A disazo-dyestu'fi which is free from sulfonic acid groups and corresponds to the formula in which R2 stands for a benzene radical in which vioinal to one another.

N-C-CHa in which R2 stands for a benzene radical in which the N=N- and the OH groups occupy posi- H 0--CH3 tions vicinal to one another and Y stands for a H3CO=N N=CCH3 l Q QQ QL 2) 1H sulfonic acid amide group bound by the acid radical to R2.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Number 7. The disazo-dyestufi of the formula the -N=N-- and OH- group occupy positions 5. The disazo-dyestuff of the formula N=C--CHs NzN 6. The disazo-dyestuff of the formula N=CCHa WILLY WIDMER. 

4. A DISAZO-DYESTUFF WHICH IS FREE FROM SULFONIC ACID GROUPS AND WHICH CORRESPONDS TO THE FORMULA 